Manufacture of cementitious materials



106. COMPOSITIONS, 8 7,

e; COATING R PLASTIC. x p n Patented June 6, 1933 p I l E I UNITED STATES PATENT OFFICE ALTON BLANK, OF PUEBLA, MEXICO, ASSIGNOR TO CEMENT PROCESS CORPORATION, A CORPORATION OF DELAWARE MANUFACTURE OF GEMENTITIOUS MATERIALS No Drawing. Application filed November 23, 1932 Serial No. 644,084.

This invention relates to the manufacture' nous com onents of the argillaceous mateof cementitious materials, and more particu- 1 mal. Zpependmg on the duration of the treatlarly to anew process whereby such materials men the temperature and the kinds and may be produced at a relatively low cost as proportions of the calcareous and siliceous 5 compared with the present processes and with or argillaceous materials used, the resulting strength and other physical properties adproduct may be on the one hand similar in justed as desired in order to meet any one of composition and have physical properties a wide variety of industrial applications, equal to those possessed by the best grades The invention also includes the new cementiof Portland cement, and in some cases equal- 13 tious products that may be produced by the ling or exceeding those possessed by the soprocess. called super cements and other high-grade The processes heretofore commonly emhydraulic cements nowavailable. On the ployed for preparing hydraulic cements of other hand, a product having properties.

the types known as Portland cement and which make it particularly adaptable for use I super cement have included as an essential as a mortar or as a relatively low-grad as step the calcination to incipient fusion of cement may be oduced. an intimate and properly proportioned mix- I have found furtheiy'that the addition of I g ture of calcareous and argillaceous materials. varying amounts ofPoi'tland cement or Port- This operation involves a large initial outland cement clinker an e grin ng or lay for kilns and related apparatus and a conmg of the same with the calcareoi andtinuing relatively high cost for repairs and siliceous, or argillaceous materials 0 e" maintenance of the apparatus employed. In types above mentioned, under the controlled addition, there are substantial operating low temperature and moisture conditions costs for fuel and power. The product of above mentioned effects a marked enhancethe calcination treatment must be re-ground, ment in the strength properties and other dethus further adding to the cost of manufacsirable physical characteristics of the cementure. titious products produced.

. Th l i ti tr t ent bov I have still further found that when certioned has been regarded as essential in order tain so-called catal zin and accelerating w to bring about such chemical combinations a entsare adde at an appropria e s age 1 between the lime constituent and the siliceous tlie process there is a further marked imand aluminous components of the argilla provement in the properties of the finished ceous material as will insure to the product product. the hydrating, strength and setting proper- More particularly, I have found that by 35 ties desired in a hydraulic cement of either using properly selected calcareous and siliof the types above mentioned. As disclosed ceous materials, or argillaceous materials of in my co-pending application Serial No. the types above mentioned, and suitably reg- 623,5 98, filed July 20, 1932, of which this ulating the temperature and moisture conapplication is in part a cor tinuationfiI have ditions during the reaction stage the silica "'Wvere a wie n'Tiiife in d Torm reactive component and the alumina component if to silica and alumina and in a line state of present, of the siliceous or argillaceous material can be either partially or completely mm brought into chemical combination with the an arm aceous ma erIa or any one o e lime component, thereby forminga resulting 45 types heretofore consldcrcd as useful in Portproduct with controlled physical and chemland cement manufacture, under controlled ical properties. The reaction of therlrirnaand low temperature conditions and in the presthe siliceous and aluminous compo ents apcnce of water or water vapor, the lime will pears to take place when the lime, if intro- 5 enter into chemical combination with the duced as uick lime, has been brou ht to the 0 siliceous components as well as the alum1- hydrated'state and to be accompanled by the p I v t liberation of water. When conditions are so controlled as to substantially completely react the siliceous and aluminous components with lime, the resulting product will ordinarily contain only an extremely small pro portion of free water, usually less than 1%, and only a minor proportion of the combined water originally present in the siliceous or argillaceous material used and in the calcareous material, if this material is introduced in the form of lime hydrate. The presence during the reaction stage of free water either as such or in the form of steam appears to be essential to bring about the desired combinations between the lime and the silica and alumina. On the other hand, for the production of a satisfactory product, it is not essential that the reactions be carried to the point where the greater part of the combined water originally present shall have been removed.

I have found that, in the presence of a limited amount of water, water va )or or steam. lime, whether introduced as gtu iEE-me.

- o 1 ,as the hydi ate, can be caused to react with the siliceous cdmponents"of a siliceb iisinaterial, the siliceous andaliiminous compo;

nents of an argillaceous material, over a relatiye l wide temperaturerange. I lie reaction at fitfipeia'uri-esterew ate boiling oint of water is relatively 'slow 'aiit'l iiicoin plete but iiia'y be increased to some extent by resort to extremely fine grindin of the operation, is not removed so rapidly tem eratures and vigorous stirring of the material's duruig the treatac r siliceous materials, such for example as sand, or materials of an ar illaceous nature, are to be used, they shoimfdffid, either preliminarily or in the course of the process, more finely than has been the general practice when they are used in making Portland cement according to the high temperature process.

I am aware of the fact that it has been proposed heretofore to bring about chemical combinations between lime and alumina by slaking quick lime in the presence of certain highly aluminous clays. However, in this prior art care was taken to avoid the use of materials containing large amounts of silica. By contrast my process has for an object to bring about combinations between the lime and the siliceous components of the siliceous clay or other siliceous material employed whereby a product possessing the setting and strength characteristics of materials containing calcium silicates is obtained.

My experience confirms the opinion prevailing in the art, that alumina reacts relatively easily with lime to form quick setting 99 compounds, whereas silica is relatively inert, but when brought into combinations with lime produces compounds which on setting exhibit high strength. My investigation show that sili ca as existing in naturally occ e cl tTs or siliceous materials either does not react with lime when mixed there- 'f"nrteinpera'turee 61' re W w ly"atoiiialteitiiiipiacticable to attempt to produce compounds having satis- 109 factory setting properties and strength by merely mixing the materials at ordinary temperatures. It was only after extended investigations that I was led to the discovery that silica is reactive with lime to a satisfactory g e roiifl lit'iiito intimate relation therewith at mgderate ly elevated provided such N contact I 15" as to be ineifective in aiding in promoting the elfec ed iii the presence of moisture and 45 desired reactions, the operating temperatures should not be carried to above say around 400 C. The temperature values above indicated are to be understood as meaning the temperature of the exciting product taken as under a'ppropfiate cofi d trons asTo lnter- 119 Hfitmsafiv' components. I am also aware of the fact that it has been proposed to increase the rep activitv of silica toward lime b sub'ectin it leaves the tube null or other grinding or 51 lceous matena s to awpre lminary ca i mixing apparatus used for effecting the desired reactions. The temperature in the reaction zones will be somewhat higher.

IVhile any of the siliceous material or argillaceous materials commonly used in cement manufacture may be employed, I have found that particularly advantageous results have. been obtained with materials that in their natural state or after a small amount of grinding, are reduced to a fine state of subdivision. Materials possessing this physical characteristic are tri oli and diatomaceous earth. These materlas reduce easily to a fineness of at least 90% 65 through a QOO-mesh screen.

When other 7 tion treatment. However, I have established by careful investigation that even with such preliminary calcination treatment, silica does not react with lime at low temperatures 120 sufliciently rapidly or to such an extent as to produce a product having the setting properties and strength characteristic of cements containing calcium silicates, and that even at moderately elevated tempera- 1 5 tures, say of the order of around 100 to 400 no practical result is obtainable unless the materials are suitably comminuted, either preliminarily or in the course of the operation, and sufiicient water is supplied to I06. COMPOSITIONS,

COATING OR PLASTIC.

insure the presence of moisturerin the reaction zone throughout the course of the operation.

The practice of the invention will be illustrated by the following examples:

Caustic lime and diatomaceous earth in the proportions by weight of two ats f lime to one part di, W v In ca culate on a ry asis were in -IO( ced into a tube mill and subjected to a grindin an d .mi.xi.ngsaction in accordance with normal grinding practice. The diatom-aceous earth contained about of its dry weight of free wateg Sufiicient additignal water was added to 1nsure compIt et-e hydration of the lime and to insure that the grinding was carried out continuously in the presence of moisture, but at the same time did not produce wet grinding conditions. The temperature of the materials introduced was approximately 22 C. The operating conditions were so contro e that the temperature of the product existing attl' ggljsghar e end of the mill was approximately 120 i Q Ihis control was effected by reguIating the feed rate of the charge materials. Varying amounts of Portlgnd cement were admixed with the materials 111 1e tube mill and samples of the resulting product obtained and tested. Sample products containing no Portland cement were also obtained and tested. I set forth below the tensile strength values and setting times of the several products together with percentage comparisons of the same with a representative high-grade Portland cement composition It will be observed from the above that the product containing 12.6% of Portland cement shows strength values approximately 16% greater than a representative high-grade Portland cement and, therefore, of the order of a super cement. Still higher percentages of Portland cement additions up to around and even more, if desired, are recomrequired.

it for use either as a mortar or as a high quality plaster. TVith additions of Portland cement of around 5 to 10% a high-grade mortar can be produced.

In another test run caustic lime and tri oli in the proportions by weight OI two parts 0 gl'lereinbefore described.

Examinei lime to one part of tripoli were mixed with wategjn a, hydrator consisting of a long screw conveyor and to which the materials and water were added at one end and from which the hydrated lime and tripoli mix was introduced directly into a tube mill while heated as a result of the hydrating reactions. An excessof water was added in the hydratoi sulfi- .mae-

ment to insure the presence of moisture in the Tensile strength values in lbs. settmg arisen (hours and Percent per sq inch (1.3 sand) I pep mmutes) cement cent in test with sample Port- 24Hrs. 3 Days 7 Days 28 Days land Initial Final cement The results of these tests go to show that in practising this embodiment of the invention and with the siliceous material indicated very satisfactory mortars and stgccos may be produced by adding from 10 to 2 O of Portland cement in the course of the operation; that with additions of Portland cement of, say a product having early strength and other desired properties equal to those of a hi h-grade Portland cement may be produced; and that misi'rntroee: land cement addition constitutes to 90% of the final product, such product will have the characteristics of a stage; cement- Instead of mixing the siIioii material ;with the lime prior to the hydrating step as in the next precedin example I ma h "dra h se ara tel and then adi'ii't dg s1 ice'iiiis iiiateria to the hydra e nne n TiTifiiBe mill.- 'Tests that have been made. with diatomaceous earth and with tripoli ;show that the results obtainable by operatjing in. this manner, both with and without mended where still higher early strengths are Y W M The product containing no Portland cement addition possessed the physical; properties and other characteristics adapting the further addition of varying amounts bf Portland cement, are equally as good and in marfisflietter than those so far obtained by practising the invention in the ways When the hydra- ";tion is carried out in a separate step from the final mixing and grinding in the tube inill, it is preferable to pass the hydrated material directly to the tube mill without permitting it to cool, thus conserving the Heat W- of hydration and thereby helping to mainof siliceous materials such as diatomite and tain the optimum temperature conditions for t-ripoli. In the tests so far conducted with promoting the desired reactions in the grindclay it has been found that a good grade of ing and mixing stage in the tube mill. Sirnimortar may be produced when small addilar modifications may be made when using tions of Portland cement have been made. any of the argillaceous materials hereinbe- In order to produce a product having the fore mentioned. desired physical properties of Portland ce- In another test air slaked lime, tripoli and ment, an addition of approximately 50% of water were mixed in the screw coni 'e'yo'i" hy- Portland cement to the other materials treatdrator and then treated in the tube mill. ed in the process is recommended, and for the Sufiicient water was added to insure the production of a super cement of good quality presence of moisture throughout th grinda 75% addition of Portland cement would be ing operation in the tube mill, but insufficient needed.

water was added to produce wet grinding Mixtures of diatomaceous earth, tri )Oll conditions. The temperature of the tube and clav, andmmmaceous mill operation was so controlled as to ini i sure a temperature in the exiting material of approximately 150 C. The lime used in easamnt' wiai"satisfactor results; As this test had been burned in l jli jilm i lg hereinbefore more generally indicated, our and contained a high percentage of the sult t h v h wn that the process is capable phate and the S1ll)l1i(lC of lime, whereas the of application to a wide variety of argillat t had 5 lime used in earlier es s cen burned in ceons materials, a rotary k ln and contained only a trace of w- As previously stated herein, I have found these constituents.

The TeSultS Of this test that the use of certain agcelerating or imwere in some ways still more interesting than provinn' a t appears 0 6 9C a ar-RBFFQO ML. those of the previous tests. Based on test 1m1-ease, 111 {F5 t th bt d d 111 strength data up to and including 7-day di up f th tti f th d t, strength figures, the product produced both A t f thi t th t I h f d t i without Portland cement additions and with prove th ili or ili d t f thi varying cement additions showed the followprocess are di lt l i hl id t- Percentage Compared with the sodium hydroxide amannic acid. am Portland cement used as a basis of comaware 0 19 ac t m d th parison in the tests hcreinbefore set forth in agents d th agents th t may b dg -e detail: ed as equivalent thereto for effecting cercumpm tain improvements in the setting and Percent son in strength propertles of cementitious mate- ,EPQZQ, age, rials. However, the results obtained by me Sample 22 35; in my investigations go to show that such agents produce in the products of my process 92 2 a much greater degree of enhancement of 42160 121.0 desired physical properties than might have 310 been predicted from their eflect on the cementitious materials with which they have Th results f thi t i di th an heretofore been used. I believe that this is addition of around 30% of Portland cement due at In P 9 the fact that these would insure a finished product giving the agents are 'h h lhto y P at normal strength values for Portland cement. dlffelfeht st'age 1h lts manufacture and under I'Vith larger additions a product having the cohdltlhhs radmany dlfiereht from those high early strengths of a super cement may def Whlch y i used by the Prlor be produced. The superior strength values Th adfhtloh of these agents to of the products of this test as compared with y p h 1S e s made t suhlect of 21 those hereinbefore mentioned for a lime-tripco'pehdlhg apphcahloh seljlal 1 8 Oh mix are believed to be in part due to the filed 1932, Wherelh I am settmg presence of calcium carbonate that had been forth examples of speclhc testsformed in tmslaking period, and in part to the presence of sulphur either as sulphate or sulphide, in the lime, and to beneficiating effects produced by these compounds in the course of the grinding and mixing operations of the process.

described,

In addition to the products with properties of the order of those of Portland cement and su er cements, products having plasticity and sprea ing qualities adapting them for use as high-grade mortars and may be produced. In tns Eonnection, it has been observed that the products In addition to the tests above other tests have been conducted with clay produced either without any Portland ceand with river sand which indicate that the ment addition or with small additions, say, process is no 1m1 ed in its application to less than 10%, show strikingly high inspecially selected relatively high-grade types creases in strength in the period from 7 to 106. COMPOSITIONS, i

COATING OR PLASTIC.

28 days. In other words, the mortars possessing either low or normal strengths at the end of 7 days show strengths at the end of 28 days far superior to those possessed by the mortars now commonly available and having similar strength properties at the end of 7 days.

In further explanation of the strength values and the setting times observed and set forth in the tables hereinbefore present ed, I would point out that the tests there recorded were all carried out in accordance with American standard methods for testing Portland cement. This involved, for the strength tests, holding the test samples in air for 24 hours and'then immersion in water for the other periods. It will be understood that this method would not be productive of such high strength values for the mortar compositions as would have been the case if such samples had been tested under the standard conditions laid down for testing mortars. For the purpose of better evaluating the testproducts that showed promise as mortars rather than cements, a series of strength tests was run wherein the test samples were stored for one day in the air and then for 3, 7, and, in some cases, 28 days in moist air, i. e., they were disposed in a closet above a pan of water so as to insure humid conditions. These tests were uniform in showing markedly higher strength values than were recorded in the tests made according to the Portland cement testing method.

In the test runs referred to herein, the tube mill employed was of standard type having an internal diameter of 5 feet and a length of 22 feet, and provided with grinding media examine? degree of fineness before they are mixed. Therefore, agitating and mixing apparatus that will insure a thorough and rapid mixing of the materials may be substituted for the grinding mill in case the materials are brought to the operation in a state of fine subdivision.

The degree of fineness to which the materials should be brought either before or during the mixing operation will vary to some extent with the materials and with the type of cement that it is ultimately desired to produce. When producing a product having a high strength and quick hardening properties superior to those possessed by ordinary Portland cement or similar to or even exceeding those of the super cements now available, materials should be used that have a relatively high degree of fineness. This condition is satisfied when either diatomaceous earth or tripoli is used. Themi mfit'i through a 325-mesh sieve. Likewise, tripoli is easily reduced to a fineness of about 95% through a. QOO-mesh sieve and through a 325-mesh sieve. These finenesses were possessed by the diatomaceous earth and tripoli used in the tests hereinbefore described. If other siliceous materials or argillaceous materials are used for the purpose of producing products having superior properties of the kind above mentioned they should be brought to a degree of fineness of the order specified. In producing products of given strength values, the proportion of Portland cement addition may be reduced by using ortland cement tha 1 7:

' an 1s e customary practice. 11 making the Portland cement addition,

consisting of cylindrical metal slugs of about it imp tant to Be f iifiiiiild that -such at," diameter and 1 A in l th, It ill addition when made in the form of finely be understood that other forms of grinding ground m n must e made at a point suband mixing apparatus may be employed 6 A MM A which will insure a similar degree of grindavlng the g""' "0fihi "iiropertles of a ing and mixing. Portland or super cement is to be obtained.

It will be understood that the tube mill 0therw1se thesettmg propertles of the P operations referred to above are cited merely will he detroyed in h hydrating g by way of example. There are obviously If the hydration of the lime is to be carried many other methods and means for efi'ectlih m hfi j ih h i flfily wlth ing the desired intimate mixture of calcare- 'g g nd mlxl'hg lllcmtnf l' fi l s guent tp the hydrating step if a prom" 7r 1613s. .4 1 a,,- r ous and siliceous or arglllaceous materlals of the 111116 with the Sihceolls 5111090115 and in the presence of moisture and with conah1m1hllS,0mP0h6I1tS P i s'pref rtrolled temperature conditions. In lieu of flble to make Lrfland m n addltwn a tube mill such as described, other types of 111 the form P Chnkel' 3 Y grollha C grinding mills and agitating and mixing y,9 2 q u devices may be used provided steps are taken In addltloh t0 the desllahle PI P QS to insure the presence of moisture and con- Possessed X YP h have h heret l f th temperature i th Operation tofore mentioned, would further point out within a range promoting the desired reacthat Product y be Produced that 18 chartions, acterlzed by a higher degree of plasticity When the tube mill or another grinding than is po se ed by Portland cement and mill is employed some grinding takes place ha g s a c q ence go d water-pmof along with the mixing of the materials. properties even without the addition of any However, grinding is not essential provided substance designed to 1mpart water-proofing the materials have been reduced to a sufficient pr p rties.

er se but also water vapor and steam.

It is also within the scope of the invenat an intermediate stage in the operation'fas for example in the hydrator or in the tube mill. Tests have shown that rosin up to approximately 2% by weight of the final product is eifective in imparting water-proofing properties. Other resins or organic materials capable of forming resmates wi t e ime component 0 t 1e mixture may e use further characteristic of this type of product when it is prepared by the use of a siliceous material such as one of the intusorial earths, e. g., diatomaceous earth or tripoli, is its relatively low specific gravity. Cement products may be produced by the use of diatomaceous earth with a specific gravity of around 2.3. Products may be produced by the use of tripoli with a specific gravity of around 2.6. These figures compare with the specific gravity of ordinary Portland cement of around 3.1 and consequently point to another advantage of my product in situations Where high strength with reduction of weight is a consideration.

My process has the further advantage that it makes possible the production of products of different color shades up to and including white by properly selecting the materials used.

The term water as used in the claims is to be understood as including not only water will he understoh d that various modifications may be made in the details of the procedure and in the proportions and kinds of materials employed without departing from the spirit of the invention which is not to be deemed as limited other than as indicated in the appended claims.

I claim:

1. The process of producing a cementitious product which comprises mixing lime in a form reactive to silica and alumina with a material selected from the group consisting of silica sands, siliceous earths and clays, and other argillaceous and argillo-calcareous materials generally known to be suitable as the raw materials for supplying the siliceous and aluminous components in Portland cement manufacture, and previously reduced to a fineness of approximately 90% through a 200-mesh screen or finer, said mixing being carried on in the presence of an amount of water sutficient to insure hydration of any quick lime present and suiiicient to insure the presence of free moisture in the mixture throughout the mixing operation, and, while mixing, iaintainingihemix t a temperaturefbout 100 C. or more to goduce mutual re ioiis betw efi' 'the T1iY1e' d the siliceous components of said material.

2. The process of producing a 'cementitious product which comprises mixing lime in a form reactive to silica and aluminawith a material selected from the group consisting of silica sands, siliceous earths and clays, and other argillaceous and argillo-calcareous materials generally known to be suitable as the raw materials for supplying the siliceous and aluminous components in Portland cement manufacture, and previously reduced to a fineness of approximately. 90% through a 200-mesh screen or finer, said mixing bein carried on in the presence of an amount 0? water suificient to insure hydration of any quick lime present and sufficient to insure the presence of free moisture in the mixture throughout the mixing operation, and, while mixin intainin ixture at a temperatur 5f atleast 100 C. produce mutual reactionsbetWeerIthdliiTie and the siliceous components of said material.

3. The process of producing a cementitious product which comprises grindin lime in a form reactive to silica and alumina with a material selected from the group consisting of silica sands, siliceous earths and clays, and other argillaceous and argillo-calcareous materials generally known to be suitable as the raw materials for supplying the siliceous and aluminous components in Portland cement manufacture, in the presence of amount of water while maintaining ture at a temperature of about 100 C. or more to produce mutual reactions between the lime and the siliceous components of said material,

.and continuing said treatment until the mixture has been reduced to a state of subdivision of approximately 907o through a 200-mesh screen or finer.

4. The processof producing a cementitious product which comprises grinding lime in a form reactive to silica and alumina with a material selected from the group consisting of silica sands. siliceous earths and clays, and other argillaceous and argillo-calcareous materials generally known to be suitable as the raw materials for supplying the siliceous and aluminous components in Portland cement manufacture, in the presence of a limited amount of water while maintaining the mixture at a temperature of at least 100 C. and

not exceeding about 400 C., asuneasured by the t-emperatui'eofthe product exiting from the grinding zone, to produce mutual reactions between the lime and the siliceous components of said material, and continuing said treatment until the mixture has been reduced to a state of subdivision of approximately 90% through a 200-mesh screen or finer.

5. The process of producing a hydraulic cement which comprises grindingl im e in a form reactive to silica and alumina with a material selected from the group consisting of silica sands, siliceous earths and clays, and other argillaceous and argillo-calcareous materials generally known to be suitable as the raw materials for supplying the siliceous and aluminous components in Portland cement COATING OR PLASTIC.

manufacture, in the presence of a limited amount of water while maintaining the mixture at a temperature sutficient to produce mutual reactions between the lime and the siliceous components of said material, and continuing said treatment until the mixture has been reduced to a state of subdivision exceeding approximate 90% through a 200- [stardust able as the raw materials for supply the siliceous and aluminous components in Portland cement manufacture, and previously reduced to atiznressnfanm eim y through a 200-mesh screen or finer; in the presence of w -"a't'r to efi'ect hydration of the lime, and continuing the mixing in the presence of an amount of water sufficient to inniesh screen or finer'an Tifitiltlflimfialidp suee the presence of free moisture through- 10 the silieo'us'compo ents, and as well, any;

cement- FM 7. The process of produclng a cefrifitfizious g aluminous components present, have been,

brought into chemical combinations such thati the product will show the hydrating and setj ting properties characteristic of a hydraul' cement. v

6. The process of --produ cing a hydr llic cement Which comprises grinding in a form reactive to silica and alumina with a material selected from the group consisting of silica sands, siliceous earths and clays, and other argillaceous and argillo-calcareous ma terials generally known to be suitable as the raw materials for supplying the siliceous and aluminous components'in Portland cement manufacture, in the presence of a limited amount of water while maintaining the mixture at a temperature of at least C. and not exceeding about 400 C., as measured by the temperature of the product exiting from the grinding Zone, to produce mutual reactions between the lime and the siliceous components of said material, and continuing said treatment until the mixture has been reduced to a state of subdivision exceeding approximately 90% through a. 200- mesh screen or finer, and until the lime and the siliceous components, and zpsl lll 5 1 f), aluminous components "present' have been brought into chemical combinations such that the product will show the hydrating and setting properties characteristic of a hydraulic product which comprise bringing together limefiith a finely divided material from the group consisting of silica sands, siliceous earths and clays, and other argillaceous and argillo-calcareous materials geny te ment which comprises mixing caustic lime' with a material selected from tEegrou'F sisting of silica sands, siliceous earths and clays, and other argillaceous and argillo-calcareous materials generally known to be suitout'the mixing operation, and, while mixing, maintaining the mixture at a temperature of ilhQl l lQw. or more to produce mutual reactions between the lime and the siliceous components of said material until the lime and the siliceous components, and as well, any aluminous components present, have been brought into chemical combinations such that the product will show the hydrating and setting properties characteristic of a hy draulic cement.

9. The process of producing a cementitious product which comprises mixing caustic lime and a material selected from them sisting of silica sands, siliceous earths and clays, and other argillaceous and argillo-calcareous materials generally known to be suitable as the raw materials for supplying the siliceous and aluminous components in Portland cement manufacture, in the presence of sufticient water to effect hydration of the lime, liren grinding the resulting mixture in the presence of a liniited ainount of water while maintaining the mixture at a temperature sufficient to produce mutual reactions between the lime and the siliceous components of said material, and continuing said treatment until the mixture has been reduced to a state of subdivision of approximately 90% th ough a 200mesh screen or finer.

{10. The process of producing a cementitious product which comprises mixing hycof'rfisting of silica sands, siliceous earths and clays, and other argillaceous and ing the siliceous and aluminous components in Portland cement manufacture, and previously reduced to a fineness of approximately 90% through a QOO-mesh screen or finer, in the presence of an amount of water sufficient to insure the presence of free moisture throughout the mixing operation, and, while dratecllime and a material selected from the 15 and intimately ,mixing fine y diV'ided-caustie. .argillo-calcareous materials generally known We) be suitable as the raw materials for supplymixing, maintaining the mixture at 'a'tem perature sufiicient to produce mutual reactions between the lime and the siliceous components of said material.

11. The process of producing a cementitious product which comprises rinding air slaked lime and a material selec t ed'fr oiirthel group co nsisting of silica sands, siliceous earths and clays, and other argillaceous and argillo-calcareous materials generally known to be suitable as the raw materials for supplying the siliceous and aluminous components in ture of lime in a form reactive alumina 211M a material selected from the aremismaierial conta ning lime in a form re- 5 and the siliceous components of said material,

and ontinuing said treatmeuiquntil themixture has been reduced to a state of subdivision "of approximately 90% through a 200-mesh screen or finer.

'tious product which comprise group consisting of silica sands, siliceous earths and clays, and other argillaceous and argillo-calcareous materials generally known to be suitable as the materials for supplying the siliceous and aluminous components in Portland cement manufacture, by mixing them in the presence of water and maintaining the mixture at a temperature of about 100 C'. .or more to produce mutual reactions between the lime and siliceous components of said material, and adding Portland cement 12. The process of produc'ng a 95311129161- ormmg a mix- -Si1lC21 and and aluminous components in Portland cement manufacture, and with Portland cement in the presence of Water, while maintaining the mixture at a temperature suflicient to produce mutual reactions between the lime and the siliceous components of said material and continuing saidtreatment until the mixturehas been reduced to a state of subdivision of approximately 90% through a QOO-mesh screen or finer.

16. The process of producing a hydraulic cement which comprises grinding a calcaactive to silica and alfifii iha w itli a material selected from the group consisting of silica sands, siliceous earths and clays, and other argillaceous and argillo-calcareous materials generally known to be suitable as the raw materials for supplying the siliceous and aluminous components in Portland cement manufacture, and with Portland cement in the presence of water, while maintaining the mixture at a temperature sufficient to produce mutual reactions between the lime and the siliceous components of said material, and cont-i1 do said treatment until the mixture ias en reduced to a state of subdivia material selected from the group consisting 30 of silica sands, siliceous earths and clays, and

other argillaceous and argillo-calcareous materials generally known to be suitable as the raw materials for supplying the siliceous and aluminous components in Portland cement manufactured and with Portland cement in the presence of water, min maintaining the mixture ata temperature suf iicient to produce mutual reactions between the lime and the siliceous components of said material.

14. The process of producing a cementitious product which comprises mixing lime sion exceeding app r oxiniately 0% through a 200-mesh screen and until the lime and the siliceous components, and as well, any aluminous components present, have been brought into chemical combinations such that the product will show the hydrating and setting properties characteristic of a hydraulic cement.

"17. The process of producing a cementitious product which comprises mixing causti c lipic with a material selected from the groupfc onsisting of silica sands, siliceous earths and clays, and other argillaceous and argillo-calcareous materials generally known to be suitable as the raw materials for supin a form reactive to silica and alumina m ing the siliceous and aluminous compoa material selected from the group consisting of silica sands, siliceous earths and clays, and

other argillaceous and argillo-calcareous materials generally known to be suitable as the raw materials for supplying the siliceous and aluminous components in Portland cement nents in Portland cement manufacture, in the presence of suflicient water to effect hydration of the lime, and then mixing the resulting product with Portland cement in the presence of a limited amount of water, and while mixing maintaining the mixture at a manufacture, and previously reduced to a temperature sufficient to produce mutual refineness of approximately soyt'thrgu' lra 200- actions between the lime and the siliceous mesh screen or finer, and with Portland ce-'components of the said material until the ment in the presence of water, and, while lime and the siliceous components, and as mixing, maintaining the mixture atatemper- .well, any aluminous components present,

ature sufiicient to produce mutual reactions have been brought into chemical combina- 190 between the lime and the siliceous components tion such that'the product will s 'ow the hyof said material. drating and setting properties characteris- 15. The process of producing a cementitic ofa hydraulic cement. l

hms product which comprises grindinglir nMS. The process of producing a cementiin a form reactive to silica and aluminawith tious product which comprises mixing caus- 12 a material selected from the group consisting tic lime and a material selected from tie of silica sands, siliceous earths and clays, --"g roiip consisting of silica sands, siliceous and other argillaceous and argillo-calcarious earths and clays, and other argillaceous and materials generally known to be suitable as argillo-calcareous materials generally known the raw materials for supplying the siliceous to be suitable as the raw materials for sup- 106. COMPOSITIONS, tau-muss COATING R PLASTIC.

plying the siliceous and aluminous compofacture, in the presence of water, while mainnents in Portland cement manufacture, with taining the mixture at a temperature sufii- {7" coarsely 'rgund Portland cement in the prescient to produce mutual reactions between the L ence of sufficient water to effect hydration lime and the siliceous and aluminous com- 5 of the lime, and then grinding the resulting ponents of said material, and continuing said mixture in the presence of water while maintreatment until the mixture has been reduced taining the mixture at a temperature suflito a state of subdivision of approximately cient to produce mutual reactions between 90% through a 200-mesh screen or finer. the lime and the siliceous components of said "\i 23. An improved cementitious product qnaterial. produced by grinding lime in a form reactive &19. The process of producing a cementito silica and alumina with a material setious product which comprises mixing causlected from the group consisting of silica tig limeand a material selected from the sands, siliceous earths and clays, and other group consisting of silica sands, siliceous argi'llaceous and argillo-calcareous materials 15 earths and clays, and other argillaceous and generally known to be suitable as the raw argillo-calcareous materials generally known materials for supplying the siliceous and to be suitable as the raw materials for supaluminous components in Portland cement plying the siliceous and aluminous compomanufacture, and with Portland cement in nents in Portland cement manufacture, in the presence of water, while maintaining the 1 the presence of sufiicient water to effect hymixture at a temperature suflicient to pro- 7 dration of the lime, and then indin the duce mutual reactions between the lime and resulting mixture with Portlarfiwfifi if in the siliceous and aluminous components of I the presence of water while maintaining the said material, and continuing said treatment mixture at a temperature sufficient to prountil the mixture has been reduced to a state 25 duce mutual reactions between the lime and of subdivision of approximately through 90 the siliceous components of said material. 11 2 4118811 Screen or finer.

"\{20 The process of producing a cementi- 24. A hydraulic cement product having tious product which comprises mixing hythe setting characteristics of a Portland cedratedlin eand a material selected fronTtWment and early strength properties exceeding 30 group consisting of silica sands, siliceous those of Portland cement, the said cement earths and clays, and other argillaceous and product consisting of an intimate admixture argillo-calcareous materials generally known of from W with the to be suitable as the raw materials for supbal e principally a product produced by plying the siliceous and aluminous c0mpogrinding lime in a form reactive to silica 35 nents in Portland cement manufacture, and and a umina With a material selected from previously reduced to a fineness of approxithe group consisting of silica sands, siliceous mately 90% through a QOO-mesh screen or earths and clays and other argillaceous and finer, with Portland cement in the presence argillo-calcareous materials generally known of water, and, whilenrix'rginaintaining the to be suitable as the raw materials for supmixture at atemperature sufiicient to produce p ying the siliceous and aluminous commutual reactions between the lim and th ponents in Portland cement manufacture, in siliceous components of said material. the presence of water, while maintaining the 21. The process of producing a cementimixture at a temperature of about 100 C.

tious product which comprises grindin air or more to produce mutual reactions between I from th I} 45 l k ili d a t i l l te e the lime and the siliceous and aluminous comv group nsi ting of ilica and ili us ponents of sald materlal, and continuing said earths and clays, and other argillaceous and treatment until the mixture has been reduced argillo-calcareous materials generally known t0 a State of Sub-division of approximately to be suitable as the raw materials for sup- 90% through a 200-.mesh screen or finer. plying the siliceous and aluminous compo- 5. The process of producing a cementinents in Portland cement manufacture, with tiOUS PIOdHCt W ich comprises iXin lime Portland cement in the presence of water, in a form reactive to silica and a umm with while maintaining the mixture at a temperaa siliceous earth previously reduced to a fineture suflicient to produce mutual reactions ness of approximately 90% through a 200- 55 between the lime and the siliceous compomesh screen or finer in the presence of an nents of said material. amount of water sufficient to insure hydration 22. An improved cementitious product of any quick lime present and sulficient to inproduced by rindin lime in a form reactive sure the presence of free moisture throughout to silica and alumina with a material selected the mixing operation, and, while mixing, 60 from the group consisting of silica sands, maintainingthe mixture atatemperature of siliceous earths and clays, and other argilat l ast 100 (1., and thereby effecting chem laceous and argillo-calcareous materials gcnicalcombinat'rbns between the lime and silica erally known to be suitable as the raw matecomponents of the mixture. rials for supplying the siliceous and alumi- 26. The process of producing a cementi- 65 nous component in Portland cement manutious product which comprises grinding lime 5 fecting chemical combinations between the lime and the siliceous components of the mixture.

27. The process of producing a cementitious product which comprises grinding lime in a form reactive to silica and alumina With tripoli in the presence of a limited amount of water while maintaining a temperature of at least 100 C., and thereby effecting chemical combinations'between the lime and the siliceous components of the mixture.

28. The process of producing a cementitious product which comprises mixing caustic lime and a siliceous earth in the presenceof suflicient water to effect hydration of the lime, and then grinding the resulting mixture in the presence of an amount of water sufficient to insure the presence of free moisture throughout the mixing operation, and, while mixing, maintaining the mixture at a temperature of about 100 C. or more to produce mutual reactions between the lime and the siliceous components of the mixture, and continuing said grinding treatment until the mixture has been reduced to a state of subdivision of approximately 90% through a 200- mesh screen or finer and until the lime and siliceous components have been brought into chemical combinations such that the product will show the hydrating and setting properties characteristic of a hydraulic cement.

29. The process of producing a cementitious product which comprises mixing air slaked lime and tripoli in the presence of sufcier'it water to insure hydration of the unslaked portions of said lime, and then grinding the resulting mixture in the presence of a limited amount of water while maintaining a temperature suflicient to produce mutual reactions between the lime and the siliceous components of the mixture. and continuing said grinding treatment until the mixture has been reduced to a state of subdivision of approximatelv 90% through a 200-mesh screen or finer and until the lime and siliceous components have been brought into chemical combinations such that the product will show the hydrating and setting properties characteristic of a. hydraulic cement.

maintaining the mixture at a temperature of at least 100 (1., thereby effecting chemical combinations between the lime and silica components of the mixture. 31. The process of producing a cementitious product which comprises grinding lime in a form reactive to silica and alumina with diatomaceous earth, and with Portland cement, in the presence of a limited amount of water while maintaining the mixture at a temperature of at least 100 C., thereby effecting chemical combinations between the lime and the siliceous components of the mixture. "v1 32. The process of producing a cementitious product which comprises grinding lime in a form reactive to silica and alumina with -tripoli, and with Portland cement, in the presence of a limited amount of water while mamtaining the mixture at a temperature of at least 100 0., thereby eflectin'g chemical combinations between the lime and the siliceous components of the mixture.

In testimony whereof, I have signed my name to this specification this 19th day of November 1932.

ALTON J. BLANK. 

